Method and apparatus for catalytic conversion of liquid feeds



2 1958 E. UTTERBACK 2,849,380

METHOD AND APPARATUS FOR CATALYTIC CONVERSION OF LIQUID FEEDS 5Sheets-Sheet 1 Filed llarch 31. 1954 RME/Vik/IMR 5 1 5 a l 4 T? Z 5 M4 2m L v s w H. g 8 6! a m m N Q INVENTOR flags! Z/fZerfiac/O B dZ-aM aATTORNE:

Aug. 26, 1958 E. UTTERBACK METHOD AND APPARATUS FOR CATALYTIC CONVERSIONOF LIQUID FEEDS 5 Sheets-Sheet 2 Filed March 31. 1954 INVENTO R [Ewes](/lleziark a ile TToRNEY yf 26, 1958 E. UTTE RBACK I 2,849,380

' METHOD AND APPARATUS FOR CATALYTIC CONVERSION OF LIQUID FEEDS 3Sheets-Sheet 3 INVENTOR ATTORNEY METHOD AND APPARATUS FOR CATALYTICCONVERSION Uh LllQUllD FEEDS Ernest Utterbaclt, New York, N. 51.,assignor to Socony Mobil Gil Company, Inc, a corporation of New YorkApplication March 31, 1954, Serial No. 419,958

11 Claims. (Cl. Il a-52) for conversion of high boiling liquidhydrocarbons or mixed phase hydrocarbons to lower boiling hydrocarbonsin the presence of a moving particle-form contact mass material whichmay or may not exhibit catalytic properties with respect to theconversion reaction. Typical of such processes is the catalyticconversion of heated liquid hydrocarbons to lower boiling gasolinecontaining gaseous prod ucts by the contacting of a high boiling liquidcharge at temperatures of the order of 850 F. and upwards with aparticle-form absorbent catalytic material. Other exemplary processesare the thermal visbreaking, coking or cracking of liquid or mixed phasehydrocarbon charge by contact with heated particle-form inert contactmaterials.

In such processes wherein the contact material is catalytic in nature itmay partake of the nature of natural or treated clays, bauxite,activated alumina or synthetic associations of silica, alumina or silicaand alumina to which other substances such as certain metallic oxidesmay be added in small amounts for specific purposes. When the contactmaterial is inert in character, it may partake of the form of refractorymaterials such as zirkite, corhart material, or mullite or it maypartake of the form of stones or metallic particles or balls.

This invention is specifically directed to certain method and apparatusimprovements in a hydrocarbon conversion system wherein the contactmaterial passes cyclically through a conversion zone wherein it iscontacted at suitable conversion temperatures with a liquid or mixedphase atent high boiling liquid hydrocarbon charge to effect conversionthereof and then through a regeneration or reconditioning zone whereinit is contacted at elevated temperatures with a suitable gas forconditioning said contact material to a condition suitable for reuse insaid conversion Zone.

A type of conversion system which has met with wide commercial successbecause of its practical advantages is one wherein the contact materialmoves as a substantially compact column within the conversion zone. Insuch systems it has been customary to supply the contact material intothe conversion chamber through one or more tubes extending downwardlythrough a short upper section of said chamber and terminating at thesurface of the column of contact material within said chamber. When aliquid or mixed phase hydrocarbon charge is to be converted it isdesirable to supply all or a large part of the heat required forconversion in the incoming contact material. This means that theincoming contact material and the tubes through which it enters andother metal surfaces in the upper section of the conversion vessel existat temperatures sufiiciently high to cause, upon contact by the liquidhydrocarbon charge, rapid conversion of said charge. As a result, thereis a marked tendency for coke to form on the hot tubes and metalsurfaces in the upper section of the conversion vessel. This cokeeventually 234,383 Patented Aug. 26, 1958 ice stricted passages forsolid flow near the lower end of the converter and in other portions ofthe cyclic system.

A major object of this invention is the provision in a system forconversion of liquid or mixed phase hydrocarbons in the presence of aparticle-form contact material of an improved method and apparatus forhydrocarbon and contact material introduction to the conversion Zonewhich avoids the difliculties hereinabove described.

A specific object is the provision in a continuous cyclic process forconversion of high boiling liquid and mixed phase hydrocarbon charges tolower boiling products in the presence of a moving bed of particle'formcontact material of an improved method and apparatus for distributingthe liquid charge onto the bed surface and for replenishing the bed withhot contact material while avoiding coke build up on the contactmaterial supply passages.

These and other objects of the invention will become apparent from thefollowing description of the invention.

in one form of this invention a substantially compact bed ofparticle-form contact material is maintained within a lower portion of aconfined conversion zone while a gas space (plenum space) is maintainedabove and open to the bed surface in an upper portion of the conversionzone. Liquid or mixed phase hydrocarbon charge is sprayed downwardlytoward the bed from a location or locations located a substantialdistance above the bed surface positioned centrally of the horizontalcross-section of the conversion zone. The liquid is caused to movedownwardly through only a central portion of the gas space and then thehydrocarbons pass downwardly through the bed so as to become convertedto lower boiling products existing in the gaseous phase under theelevated conversion temperature. The conversion products are withdrawnfrom a lower portion of the bed in the gaseous phase, while contactmaterial bearing a carbonaceous deposit is separately withdrawn from thelower section of the bed. Fresh contact material is supplied to the bedsurface at a suitable conversion supporting temperature through aplurality of confining passages which conduct the contact materialdownwardly to a plurality of points spaced around or near the peripheryof the bed at its surface level. The passages circumvent at least thatcentral portion of the gas space which extends between the liquid spraynozzle and the bed surface either by extending downwardly near the wallof the conversion zone housing or by completely by-passing the portionof the housing occupied by the gas space and entering the housinginitially at the level of the bed surface. In this manner contact of theliquid charge with the hot contact material supplypassages isessentially avoided.

The invention may be most readily understood by reference to thedrawings of which Figure l is an elevational view, partially in sectionshowing a form of the invention incorporating a further novelimprovement involving a central curtain of feed contact material.

Figure 2 is a sectional view along line 2-2 of Figure 1.

Figure 3 is an elevational view, in section showing the upper portion ofa conversion vessel incorporating a modified form of this invention.

Figure 4 is an elevational view, partly in section showing a preferredform of this invention.

All of these drawings are highly diagrammatic in form.

Turning now to Figure 1, we find a diagrammatic flow sketch of .acontinuous hydrocarbon conversion process. In Figure 1, there is shown aregeneration vessel 10, provided with combustion supporting gas inlet 11and heat exchange fluid inlet 12 near its lower end and flue gas outlet13 and heat exchange fluid outlet 14 near its upper end. The heatexchange fluid inlet and outlet connect into heat transfer tubes (notshown) distributed within the regenerator. Also provided is a solidmaterial inlet at the top of the regenerator and a solid material outlet16 at the lower end thereof bearing a flow control valve 32. It will beunderstood that regenerators of other construction may be substitutedfor that shown within the scope of this invention as long as suchmodified constructions permit combustion regeneration of movingparticles of spent contact mass materials at controlled elevatedtemperatures. In systems wherein the contact material is aninertmaterial, the vessel 10 may take the form of a reconditioning apparatusin whatever form may be required for conditioning the contact materialfor reuse in the conversion zone. Also shown in Figure 1 is a converter17, a supply hopper 18 located thereabove and conveyors 19 and 20adapted to transfer hot contact material particles between theregenerator and converter vessels. The conveyors may take the form ofcontinuous bucket elevators for example. Extending across the uppersection of vessel 17 is a partition 21 which serves to provide a sealchamber 22 in the upper end of vessel 17 and a conversion chamber 23therebelow. A plurality of spaced conduits 24, which may be arranged ona circular pattern as shown in Figure 2, depend from partition 21 to alevel therebelow in the conversion chamber 23. It will be noted that theconduits 24 serve as passages for solid flow from seal chamber 22 to thesurface 25 of the contact material column within the conversion chamberand that the conduits extend only through that portion of the horizontalcross-sectional area of the upper portion of the chamher which is nearthe outer periphery of said chamber. Another conduit 26 extendsdownwardly from a central portion of partition 21 to a level in theupper section of gas space 27 in the conversion chamber. A flowthrottling device is provided below the lower end of the conduit 7.6.The flow throttling device broadly consists of a plate 28 having a hole29 therein and a receiving funnel 30 positioned around the hole and aslide plate 31 therebelow which may be adjusted so that a hole 33therein coincides partially or entirely with the hole 29 in plate 28 orso as to entirely block the flow through hole 29. A rod 34 is connectedto the slide plate 31 and passes through stuffing box 35 on the vesselshell to permit adjustment of the throttling device from a point outsidethe vessel 17. The throttling device is supported by means of angleirons 36 and 37 which extend across the chamber in a directionperpendicular to the face of the drawing. Also supported by the angleirons 36 and 37 is a skirt 38 which is open on either end and positionedcentrally with its axis vertical within the vessel 17. The skirt 38tapers inwardly slightly so as to direct solid flow toward the center ofthe chamber. A conical shaped bafile 39 is supported by rods 40substantially centrally Within the skirt 38 and below the flowthrottling device. The diameter of the base of the bafile 39 is lessthan that of the skirt 38 so as to provide an annular space for solidflow therebetween. A liquid spray device 41 is positioned substantiallycentrally of the vessel crosssectional area adjacent the lower end ofskirt 38. Liquid or mixed phase hydrocarbon charge may be supplied tothe spray device 41 through pipe 42. A similar spray 43 and feed pipe 44may be provided at a lower level in gas space 27. A contact materialgravity feed leg 45 extends between hopper 18 and seal chamber 22 and aconduit 46 connects into seal chamber 22 for introduction of an inertgas thereinto. In the lower section of the vessel 17 there are providedtwo vertically spaced rows of spaced gable-roofed gas collecting troughs48 and 49. Adjacent troughs are connected by means of nipples 50, andfeed pipes 51 and 52 and 51' and 52' connect into the end troughs inrows 48 and 49, respectively. The pipes 51 and 52 and 51 and 52 are inturn manifolded into outlet pipes 53 and 53 respectively on oppositesides A bons with all the contact material.

of the vessel. Below the levels of the collector troughs are providedthree spaced partitions 54, 55 and 56. A plurality of uniformlydistributed circular rows of nipples 57 depend from the uppermostpartition 54 and a lesser number of rows of nipples 58 depend from thenext lower partition 55. The nipples 58 are horizontally staggeredproportionately between the nipples 57 thereabove. A circular row ofholes 59 are provided in the lowermost partition 56, the row of holesbeing horizontally staggered with respect to the two rows of nipplesthereabove. An outlet conduit 60 hearing fiow control valve 61 isprovided on the lower end of the vessel 17.

in operation, contact material particles are supplied from hopper 18through leg 45 into the seal chamber 22. The contact material passesfrom the seal chamber 22, through conduits 24, directly onto the surfaceof the column of contact material within the conversion chamber 23. Thetemperature of the contact material so supplied to the conversionchamber should be suitable for supporting the intended hydrocarbonconversion. Liquid or mixed phase hydrocarbon charge is sprayed into thegas space 2! from spray devices 41 and/or 43. The spray of liquidhydrocarbons is limited to the central portion of the vesselcross-sectional area. On the other hand, the conduits 24 through whichthe hot contact material charge enters are positioned only along theouter periphery of the chamber instead of being uniformly spaced.throughout the cross-sectional area of the chamher. in this manner,contact between liquid charge and hot metal surfaces in the gas space 27is limited so as to avoid the tendency for coke formation on suchsurfaces. While it is contemplated that all of the contact materialsupplied to the conversion zone may pass directly onto the surface ofcolumn 23 through the peripheral supply passages 24, which circumventthe central portion of the gas space 27, below the level of liquidspray, it has been found that the tendency for such coke formation maybe still further avoided and the distribution of the liquid charge onthe contact material may be greatly improved by also introducing contactmaterial into the upper section of gas space 27 through conduit 26 at arate controlled by the slide valve therebelow. The contact materialpassing from the conduit 26 which is horizontally centrally positionedfalls onto the conical shaped bafile 39 and falls therefrom between theannular space between bafile 39 and skirt 38 as a shower of freelyfalling particles, which shower is restricted by means of the bafiiingsubstantially to only a central portion of the gas space 27 until theparticles reach the surface 25 of the contact material columntherebelow. Liquid or mixed phase hydrocarbon charge from spray device41 and/ or 43 is sprayed into that central portion of the gas space 27within which said shower of particles is maintained so that the liquidhydrocarbon charge substantially all of the liquid charge oralternatively any portion which tends to stray toward the housing wallsis uniformly deposited upon the showering contact material particles andprevented from reaching the hot metal surfaces adjacent the outerperiphery of space 27. The contact material particles from the showersoon uniformly distribute themselves across the entire columncross-sectional area so as to provide uniform contacting of the liquidhydrocar- This latter further improvement is the subject matter ofclaims in United States Patent Number 2,574,850, issued November 13,1951. The present application is particularly concerned with the broaderimprovement of spraying liquid oil charge into the conversion zone at alocation or locations centrally disposed of the vessel horizontalcross-section and spaced above the surface of the contact materialcolumn while supplying a confined stream or streams of fresh contactmaterial directly onto the column at a location or locations near theouter periphery of the conversion under ordinary atmospheric conditions.

zone in such a manner as to avoid the path of the falling liquid oilspray.

If desired, in operations wherein the charge stock is partiallyvaporizable at the desired conversion tempera ture, the charge may besubjected to a preliminary fractionation to separate the heavy liquidportion of the charge from the vaporizable portion. Then the liquid maybe introduced in heated condition through nozzles 41 and/or 43 and theheated hydrocarbon vapor charge may be separately introduced to theconverter through conduit 8. The contact material and liquidhydrocarbons pass downwardly through the conversion zone and the liquidhydrocarbons are converted to gaseous hydrocarbon products. It will beunderstood that the term gaseous as used herein in describing and inclaiming this invention is used in a broad sense as meaning material inthe gaseous phase under existing operating conditions regardless of thenormal phase of that material Gaseous conversion products are separatelywithdrawn from the lower section of the conversion zone throughcollector troughs 48 and 49 and pipes 51 and 52, and 51' and 52',respectively. The flow in the pipes 51, 52, 51 and 52' is throttled soas to provide the proper flow of products from each row of collectortroughs. Used contact material fiows downwardly through the partitionarrangement 57, 58 and 59 in the lower end of vessel 17 and is withdrawnthrough outlet conduit 60 at a rate controlled by valve 61. Thepartition arrangement 57, 58 and 59 is in Patent Number 2,574,850,issued November 13, 1951,

the major portion of the contact material charge is introduced throughthe central conduit 26 so that most of the contact material charged maybe immediately contacted with the liquid phase hydrocarbons sprayed intothe gas space 2'7 as said contact material showers downwardly throughthe central core of said gas space. in such an operation, it isimportant to maintain the level of the surface of the column of contactmaterial substantially constant within the conversion zone. This isautomatically accomplished in the operation described hereinabove sincethe contact material flow in pipes 24 is automatically throttled only bythe column surface level. Thus, only as much contact material passesthrough conduits 24 as is required to maintain the column surface levelsubstantially at 25 as shown. In order to prevent escape of hydrocarbonvapors from the conversion zone into seal chamber 22 an inert seal gassuchas steam or flue gas may be introduced through conduit '46 into theseal chamber 22 at a rate so controlled by diaphragm operated valve 64and differential pressure controller 65 as to maintain an inert gaseousatmosphere in zone 22 at a pressure slightly higher (for example /2pound per square inch) than the pressure in gas space 27. An inert purgegas such as steam or flue gas may be introduced through conduit 67 belowpartition 54 to strip hydrocarbons from the outflowing contact material.Spent or used contact material passes via conduit 60 into conveyor 19 bywhich it is conducted to vessel 119. If the contact material is anadsorbent catalyst, air or other oxygen containing gas is introduced at11 into vessel 10 to burn the carbonaceous contaminant from the contactmaterial. Flue gas may be withdrawn at 13. A suitable heat exchangefluid introduced at conduit 12 and withdrawn at conduit 14 may be passedthrough tubes within vessel 11) which communicate with conduits 12 and14- under conditions suitable to control the regenerating catalysttemperature below a heat damaging level. For clay type adsorbents theheat damaging level vision for gaseous product and used contact materialwithdrawal from vessel 70 may be provided in its lower section (notshown) substantially as is shown for vessel 17 in Figure 1. The sealchamber 71 is separated from the conversion vessel and conduits 73 areprovided for contact material flow from chamber 71 to the surface of thecolumn of contact material in chamber '70. It will be noted that theconduits 73 do not pass through the gas space 27 within the uppersection of vessel 70 at all but enter vessel 70 only at a plurality ofpoints around its periphery substantially at the level at which it isdesired to maintain the surface of the contact material column. By thisconstruction, any chance for liquid hydrocarbon charge to contact thehot metal surface of the contact material feed pipes before the columnof contact material is reached is eliminated. Contact material may alsobe supplied, if desired, to the central portion of the convertercross-sectional area through conduit 74. The throttle device and conicalbathe below the lower end of conduit 74 are substantially the same asthose same devices shown in Figure l. The skirt 7S differs from theskirt 38 of Figure 1 in that it is not tapered inwardly, a feature whichis not in all cases necessary.

Turning now to Figure 4, there is shown an arrangement somewhat similarto that shown in Figure 3, except that the central catalyst curtain isomitted. Like elements in Figures 3 and 4 bear like numbers and will notbe further identified. In the system shown in Figure 4, the liquid ormixed phase hydrocarbon charge is sprayed downwardly through only acentral portion of the space 27, which portion is entirely free of hotcontact material supply passages and spaced a substantial distance awayfrom the housing walls. The spray may be supplied by one nozzle as shownor by a number of nozzles. In either case the nozzles should be arrangeda substantial distance above the column surface and positioned only inthe central portion of the horizontal cross-section of the gas space.The contact material is delivered to the column surface through aplurality of passages 73 which completely circumvent the gas space 27and connect into the side of converter housing initially at the surfacelevel of the column 23 and discharge the hot contact material at aplurality of points around the column periphery. The conduits 73comprise the sole means for contact material supply to the column 23 sothat not only the central portion of, but the entire gas space 27 isleft free of hot contact material supply passages.

It will be noted that the column surface converges downwardly andinwardly from the peripheral contact material feed conduits towards thecentral vertical axis of the conversion zone. Thus for a vessel ofcircular cross-section the column surface takes the shape of an invertedcone, the sides of which slope in accordance with the angle of repose ofthe contact material. The angle of repose will fall within the rangeabout 3045 degrees with the horizontal depending upon the shape and sizeof the contact material particles.

The vaporized conversion products disengage from the lower section ofthe column 23 under conical hoods 1011 and then pass via apertures 101into pipes 102 through which the vapors flow into the plenum space 103below the inverted conical shaped partition 111. If desired severalvertically spaced rows of disengaging hoods 1110 may be arranged onwithdrawal pipes 102 as shown in United States Patent 2,459,096, issuedJanuary 11, 1949. It will be understood that the hoods I? are uniformlyspaced over the entire vessel horizontal cross-section so as to promoteuniform withdrawal of vapor from all portions of the columncross-section. The conversion products in the gaseous phase leave theplenum space 103 via conduit 105. Contact material is withdrawn from thebottom of column 23 via conduits 104 which are uniformly distributedover the entire horizontal cross-section of the conversion zone. Thecontact material is delivered by conduits 104- onto bed 106 from thebottom of which it is uniformly withdrawn by pipes 107 and annularwithdrawal funnel 108. The gas withdrawal plenum system is described andclaimed in United States Patent 2,458,498, issued January 11, 1949.

It should be noted that in the arrangement modified in accordance withthe present invention the partition 11! and the arrangement of hoods 100parallel the configuration of the surface level of column 25. In thismanner the hydrocarbon reactant is caused to flow through an equal depthof the column 23 in all portions of the horizontal cross-section, inspite of the conical configuration of the column surface. It will beunderstood that for vessels of cross-sectional shape other than circularthe downwardly converging column surface will take an inverted pyramidalshape having as many sides as the confining housing.

The conditions of operation in the apparatus of this invention will varywidely depending upon the particular operational application involved.In general, the contact material should be supplied at a temperaturesuitable to support the conversion desired. This temperature will varysomewhat depending upon the particular contact material to oil ratiochosen. In catalytic cracking operations on clay-type catalysts, thecontact material charge to oil charge ratio may vary from about 1.0 to20 parts by weight of contact material per part of oil. The oil spacevelocity may be within the range of about 0.3 to 10.0 volumes of oil(measured at 60 F.) per hour per volume of contact material columnwithin the conversion zone. The contact material in the case ofcatalytic cracking operations may enter the conversion chamber attemperatures of the order of 800 F. to 1200 F., and may undergo atemperature drop of the order of F. to 300 F. in passing through theconversion zone. In the case of thermal cracking operations over inertcontact materials, the contact material temperature may be much higher.

When the central shower of contact material is omitted in the system ofthis invention, then all of the hot contact material supply will bedelivered directly onto the surface of the column of contact material inthe conversion zone.

When contact material is showered centrally through the liquid oil feedspace as well as being, supplied directly onto the column surface atpoints around its periphery, the amount of contact material enteringthrough conduits 24 (Figure 1) should be of the order of about topercent of the total contact material passed through the converter, theremainder of the contact material being supplied through conduit 26(Figure 1). In the process of this invention it has been found desirableto control the contact material particle size broadly within the range 3to 100 mesh and preferably within the range about 4 to 20 mesh by Tylerstandard screen analysis. The percentage of fines present in the contactmaterial mass should be maintained as low as possible.

The invention may be employed for conversion of hydrocarbon charge stockwhich is partially vaporizable under the conversion conditions or it maybe employed for the conversion of reduced crudes and the like whichconsist for the most part of hydrocarbons boiling above the desiredaverage conversion temperature. It is usually preferable to heat thehydrocarbon charge to a temperature of the order of 600 F. to 900 F.before introducing it into the conversion chamber.

It should be understood that the particular details of apparatusconstruction and the examples of operating conditions and processapplications of the invention given hereinabove are intended asillustrative and are in no way to be construed as limiting the scope ofthis invention except as it may be limited by the following claims.

I claim:

1. The method for conversion of high boiling liquid hydrocarbonscomprising maintaining a substantially compact column of particle-formcontact material at a suitable temperature for effecting the hydrocarbonconversion along a lower portion of a confined conversion zone,maintaining a gas space above said column in said conversion zone,spraying a high boiling hydrocarbon charge at least partially in theliquid phase into said gas space a substantial distance above thesurface of said column and passing the liquid spray downwardly throughonly a substantially central portion of said gas space, passing saidhydrocarbons downwardly into said column to effect conversion thereof tolower boiling hydro-carbons, Withdrawing hydrocarbon products in thegaseous phase from the lower section of said column separately of thecontact material, Withdrawing contact material from the lower section ofsaid column to promote downward movement of the particles therein,supplying con tact material at a suitable conversion supportingtemperature through a plurality of confined passages which circumventthe central portion of said gas space and discharge directly onto thesurface of said column only at a plurality of points near the peripherythereof, said confined passages being the only confined passagesdelivering contact material directly onto the surface of said column,whereby substantial contact of the liquid spray and the contact materialpassages is avoided.

2. The method for conversion of high boiling liquid and mixed phasehydrocarbons in the presence of a moving particle-form solid contactmaterial which method comprises, maintaining a substantially compactcolumn of particle-form contact material along a lower portion of aconfined conversion zone, maintaining a gas space in said zone above thesurface of said column, spraying a high boiling hydrocarbon charge atleast partially in the liquid phase downwardly within only a centralportion of said gas space from a location a substantial distance abovethe surface of said column and positioned only substantially centrallywith respect to the horizontal cross-sectional area of said conversionzone, passing said hydrocarbons downwardly through a portion of saidcolumn of contact material in said zone to effect conversion to lowerboiling gasiform hydrocarbons, withdrawing said gasiform hydrocarbonsfrom said conversion zone, maintaining a confined accumulation ofparticle-form contact material at a level above said conversion zone,supplying contact material to said accumulation at a temperature highenough to support the hydrocarbon conversion in said conversion zone,passing contact material through confined passages leading downwardlyfrom said accumulation and discharging the contact material directlyupon the surface of said column only at points near its periphery, whileentirely circumventing the central portion of said gas space, thecentral portion of said gas space being free of contact material supplypassages below the location of liquid spray, whereby contact of liquidcharge with confined passages for hot contact material supply issubstantially avoided, maintaining an inert gaseous blanket within saidconfined accumulation above said conversion zone to prevent fiow ofhydrocarbons thereinto and Withdrawing spent contact material from thelower section of said conversion zone.

3. The method for conversion of high boiling liquid hydrocarbonscomprising maintaining a substantially compact column of particle-formcontact material at a suitable temperature for effecting the hydrocarbonconversion along a lower portion of a confined conversion 9 zone,maintaining a gas space above said column in said conversion zone,spraying a high boiling hydrocarbon charge in the liquid phasedownwardly from a location spaced a substantial distance above thesurface of said column so that the liquid passes downwardly through onlya central portion of said gas space, leaving the surrounding outerportion of the gas space substantially free of liquid spray, separatelyintroducing a vaporized hydrocarbon charge into said gas space andpassing it downwardly toward said column, passing the vapor and liquidhydrocarbons downwardly within said column to eflfect conversion thereofto lower boiling hydrocarbons, withdrawing the lower boiling hydrocarbonproducts from the lower section of said column, withdrawingparticle-form contact material from the lower section of said column anddelivering contact material to said column at a suitable conversionsupporting temperature as a plurality of confined streams whichcircumvent the central portion of said gas space and discharge directlyonto the surface of said column at points spaced around its periphery,the central portion of said gas space being free of contact materialdelivery streams at least below said location from which the liquidhydrocarbon is sprayed.

4. The method for conversion of high boiling liquid and mixed feedhydrocarbons in the presence of a moving particle-form solid contactmaterial which method comprises, maintaining a substantially compactcolumn of particle-form contact material along a lower portion of aconversion zone which is defined by an elongated housing, maintaining agas space in said housing above the surface of said column maintaining aconfined accumulation of particle-form contact material at a level abovesaid housing, supplying contact material to said accumulation at atemperature high enough to support the hydrocarbon conversion in saidconversion zone, passing contact material downwardly from saidaccumulation through confined passages which entirely circumvent thatportion of the housing occupied by said gas space and which initiallyenter said housing at the surface level of said column so as to deliverthe contact material directly onto the surface of said column at aplurality of points spaced near the outer periphery of said column, saidpassages being the only passages for delivery of contact materialdirectly to the surface of said column, withdrawing contact materialdownwardly from the lower section of said conversion zone so as topromote downward flow of the contact material in said column, spraying ahigh boiling hydrocarbon charge at least partially in the liquid phase.into a centrally located portion of the gas space above said column,passing said hydrocarbons downwardly into said column and through aportion thereof to effect conversion of said hydrocarbons to lowerboiling hydrocarbons, withdrawing hydrocarbon products in the gaseousphase from a lower portion of said column and maintaining an inertgaseous pressure in said confined accumulation above said conversionzone at a pressure above the gaseous pressure in the upper portion ofsaid conversion zonev 5. A method for conversion of high boiling liquidhydrocarbons comprising, maintaining a substantially compact column ofparticle-form contact material at a suitable temperature for eifectingthe hydrocarbon con version along a lower portion of a confinedconversion zone, maintaining a gas space above said column in saidconversion zone, spraying a high boiling hydrocarbon charge at leastpartially in the liquid phase downwardly in said gas space above saidcolumn, passing said hydrocarbons downwardly into said column to eflectconversion thereof to lower boiling hydrocarbons, withdrawinghydrocarbon products in the gaseous phase from said conversion zoneseparately of the contact material, withdrawing contact material fromthe lower section of said column to promote downward movement of theparticles ,therein and delivering hot contact material onto said '10'column as at least one confined stream which entirely circumvents saidgas space and initially enters the conversion zone substantially at thesurface level of said column so as to discharge the hot contact materialdirectly onto the surface of said column at at least one point near theouter periphery of said column, the hot contact material beingdischarged from confined streams directly onto the surface of saidcolumn only at points near the periphery of said column as aforesaid,whereby contact of the liquid charge with the confined streams isavoided until the liquid charge reaches said column.

6. The method of claim 5 characterized in that the contact materialdischarged directly onto the column near the periphery thereof is theonly contact material supplied to said column.

7. The method for conversion of high boiling liquid hydrocarbons whichcomprises maintaining a substantially compact column of particle-formcontact material at a suitable temperature for effecting the hydrocarbonconversion along a lower portion of a confined conversion zone,maintaining a gas space above said column in said conversion zone,supplying hot contact material at a conversion supporting temperature tosaid column as a plurality of confined gravitating streams whichcircumvent the central portion of said gas space and discharge thecontact material onto the column at the lower end of said gas space at aplurality of space points near the periphery of said column, the contactmaterial discharging from said streams being the only contactmaterialsupplied to said column, whereby the surface of said column convergesdownwardly and inwardly from its periphery toward its central verticalaxis in conformance with the angle of repose of the contact material,withdrawing contact material from the lower section of the conversionzone so as to efiect downward movement of the contact material in saidcolumn, spraying a high boiling hydrocarbon charge at least partially inthe liquid state downwardly toward the column surface from only acentral location in said gas space which is spaced a substantialdistance above the column surface, the central portion of said gas spacebeing free of confined contact material supply streams, passing thehydrocarbons downwardly through said column to effect conversion of saidhydrocarbons to lower boiling products, withdrawing the lower boilingproducts in the gaseous phase from a plurality of points arranged in thelower section of said column, in a downwardly converging patternparalleling the surface of said column, whereby the depth for path forhydrocarbon flow through the column is substantially equal entirelyacross the column cross-section.

8. An apparatus for conducting the conversion of high boiling liquidhydrocarbons to lower boiling hydrocarbons in the presence of a movingparticle-form contact material which apparatus comprises, means definingan elongated conversion chamber adapted for confining a compact columnof particle-form contact material, means to withdraw contact materialfrom the lower portion of said conversion chamber, liquid spray meanspositioned substantially centrally of the cross-sectional area of saidconversion chamber near the upper end of said chamber, said spray meansbeing the only means for liquid feed within said chamber, means tosupply a liquid hydrocarbon charge to said spray means, means towithdraw gaseous material from the lower section of said conversionchamber, an accumulation chamber for contact material located above saidconversion chamber, means to supply contact material to saidaccumulation chamber, and a plurality of conduits extending downwardlyfrom said accumulation chamber and terminating on their open lower endswithin the upper section of said conversion chamber a substantialdistance below said spray means at a plurality of spaced points all nearthe horizontal periphery of said conversion chamber, said conduitscircumventing the central portion of the cross-section of 11 saidconversion chamber which is'below the level of said spray means and thecentral portion of said chamber below said spray means being free ofconduits of any type.

9. An apparatus for conducting the conversion of high boiling liquidhydrocarbons in the presence of a moving contact material whichcomprises, an elongated conversion chamber adapted to confine a columnof particleform contact material, a plurality of solid material feedconduits terminating on their lower ends at a plurality of points withinsaid chamber spaced around and near its horizontal periphery and locatedin the upper section of said chamber but substantially below its upperend, said conduits entirely circumventing the central portion of thechamber above their lower ends and being the only conduits for contactmaterial supply into said chamber, means to withdraw the contactmaterial from the lower section of said chamber, a liquid spray devicepositioned within the upper section of said chamber above the level ofthe lower ends of said solid feed conduits, said spray device beingpositioned substantially centrally of the chamber cross-sectional areaand said chamber beingfree of spray devices except in the centralportion of its horizontal cross-sectional areas, means to supply liquidoil charge to said spray device, and means to separately withdrawgaseous hydrocarbons from the lower section of said chamber.

10. An apparatus for conducting the conversion of high boiling liquidhydrocarbons in the presence of a moving contact material whichcomprises, an elongated conversion chamber adapted to confine a columnof particle-form contact material, a liquid spray device positionedwithin the upper section of said vessel centrally of the horizontalcross-sectional area of said chamber, said chamber being free of spraydevices except in the central portion of its horizontal cross-sectionalarea, means to supply liquid oil charge to said spray device, means toseparately withdraw gaseous hydrocarbons from the lower section of saidchamber, a plurality of solid feed conduits terminating on their openlower ends in a plurality of points within said chamber spaced aroundand near its horizontal periphery and spaced a substantial distancebelow said spray device, said conduits circumventing at least thatcentral portion of the chamber cross-section situated below said spraydevice so as to leave said central portion free of solid material feedconduits and means to withdraw contact material from the lower sectionof said chamber.

11. An apparatus for conducting the conversion of high boiling liquidhydrocarbons in the presence of a moving contact material whichcomprises, means defining an elongated conversion chamber adapted toconfine a column of particle-form contact material, a plurality of solidmaterial inlet conduits connecting through the side of said chamber fromthe outside thereof at a level spaced substantially below its upper endat a plurality of points spaced around the horizontal periphery of saidchamber, means to withdraw contact material from the lower section ofsaid chamber, a liquid spray device positioned centrally in the uppersection of said chamber above the level of entry of solid inletconduits, said chamber being free of liquid spray devices except in thecentral portion of its horizontal cross-sectional area and being free ofsolid material inlet conduits below the level of said spray deviceexcept as aforesaid.

References Cited in the file of this patent UNITED STATES PATENTS2,416,214 Payne Feb. 18, 1947 2,432,344 Sinclair Dec. 9, 1947 2,439,372Simpson Apr. 6, 1948 2,534,090 Weber et al Dec. 12, 1950 2,538,472Robinson Ian. 16, 1951

1. THE METHOD FOR CONVERSION OF HIGH BOILING LIQUID HYDROCARBONSCOMPRISING MAINTAINING A SUBSTANTIALLY COMPACT COLUMN OF PARTICLE-FORMCONTACT MATERIAL AT A SUITABLE TEMPERATURE FOR EFFECTING THE HYDROCARBONCONVERSION ALONG A LOWER PORTION OF A CONFINED CONVERSION ZONE,MAINTAINING A GAS SPACE ABOVE SAID COLUMN IN SAID CONVERSION ZONE,SPRAYING A HIGH BOILING HYDROCARBON CHARGE AT LEAST PARTIALLY IN THELIQUID PHASE INTO SAID GAS SPACE A SUBSTANTIAL DISTANCE ABOVE THESURFACE OF SAID COLUMN AND PASSING THE LIQUID SPRAY DOWNWARDLY THROUGHONLY A SUBSTANTIALLY CENTRAL PORTION OF SAID GAS SPACE, PASSING SAIDHYDROCARBONS DOWNWARDLY INTO SAID COLUMN TO EFFECT CONVERSION THEREOF TOLOWER BOILING HYDROCARBONS, WITHDRAWING HYDROCARBON PRODUCTS IN THEGASEOUS PHASE FROM THE LOWER SECTION OF SAID COLUMN SEPARATELY OF THECONTACT MATERIAL, WITHDRAWING CONTACT MATERIAL FROM THE LOWER SECTION OFSAID COLUMN TO PROMOTE DOWNWARD MOVEMENT OF THE PARTICLES THEREIN,SUPPLYING CONTACT MATERIAL AT A SUITABLE CONVERSION SUPPORTINGTEMPERATURE THROUGH A PLURALITY OF CONFINED PASSAGES WHICH CIRCUMVENTTHE CENTRAL PORTION OF SAID GAS SPACE AND DISCHARGE DIRECTLY ONTO THESURFACE OF SAID COLUMN ONLY AT A PLURALITY OF POINTS NEAR THE PERIPHERYTHEREOF, SAID CONFINED PASSAGES BEING THE ONLY CONFINED PASSAGESDELIVERING CONTACT MATERIAL DIRECTLY ONTO THE SURFACE OF SAID COLUMN,WHEREBY SUBSTANTIAL CONTACT OF THE LIQUID SPRAY AND THE CONTACT MATERIALPASSAGES IS AVOIDED.